Phosphonium compounds

ABSTRACT

Novel aralkyl phosphonium salts have been prepared. Compounds of this invention possess useful gastric anti-secretory, spasmolytic and anti-ulcerogenic properties. A method of treating gastrointestinal hyperacidity and ulceration has also been disclosed.

United States Patent [191 Diamond et al.

PHOSPHONIUM COMPOUNDS Inventors: Julius Diamond, Lafayette Hill; KingAuyang, Philadelphia, both of Pa.

Assignee: William H. Roi-er, Inc., Fort- Washington, Pa.

Filed: Dec. 17, 1970 Appl. No.: 99,313

U.S. Cl. 260/606-5 F, 260/465 H, 260/465 G, 260/465 F, 260/465 D,260/578, 260/577, 260/558, 260/562, 260/471, 260/469, 260/599, 260/601,260/544, 260/503, 260/556, 260/551, 260/535, 260/537, 260/513, 260/515,424/221 Int. Cl. C07f 9/54 Field of Search 260/606.5 F, 606.5 P

[ June 26, 1973 [56] References Cited UNITED STATES PATENTS 3,268,3238/1966 Goyette 260/606.5 F 3,502,725 3/l970 Dewhirst et al. 260/606.5 P

Primary Examiner-Werten F. W. Bellamy Attorney-James A. Nicholson [5 7ABSTRACT Novel aralkyl phosphonium salts have been prepared. Compoundsof this invention possess useful gastric anti-secretory, spasmolytic andanti-ulcerogenic properties. A method of treating gastrointestinalhyperacidity and ulceration has also been disclosed.

33 Claims, No Drawings PHOSPHONIUM COMPOUNDS SUMMARY OF THE INVENTIONThis invention describes new phosphonium salts and processes for theirpreparation. This invention further provides valuable pharmaceuticalpreparations which contain these phosphonium salts as gastricantisecretory, spasmolytic, and anti-ulcerogenic agents. A method forthe treatment of gastrointestinal hyperacidity and ulceration is alsodescribed.

BACKGROUND OF THE INVENTION The pharmaceutical compositions which havebeen used as anti-secretory and spasmolytic agents have been such asatropine, homatropine, propantheline bromide, dicyclomine hydrochlorideand other compounds which are structurally dissimilar to the onium saltsof this invention. Due to the anti-cholinergic properties of these knowncompounds, they produce undesirable side effects such as mydriasis,xerostomia, cyclopegia, and other unwanted effects.

There have been a number of aralkyl and alkyl phosphonium saltsdescribed in the literature with a lower alkyl group having up to fourcarbon atoms. They have mainly been proposed for use as bactericidal andfungicidal agents, and as plant growth regulators.

We have unexpectedly found novel phosphonium salts which have valuablepharmacologic properties.

We have found phosphonium salts which possess useful gastricanti-secretory, spasmolytic, and antiulcerogenic properties.

We have further found trialkyl aralkyl phosphonium salts which arenovel.

We have also found that the compounds of this invention aresubstantially void of the anti-cholinergic side effects which accompanyheretofor known gastric anti-secretory and spasmolytic agents.

We have still further found a simple and effective method for treatinggastric hyperacidity and gastrointestinal ulceration such as duodenaland peptic ulcers.

We have found a class of therapeutically effective compounds which canalso be conveniently synthesized.

DESCRIPTION AND PREFERRED EMBODIMENTS This invention provides a methodof preparing novel phosphonium salts.

This invention further provides pharmocologically active chemicalcompounds which are useful in treating gastrointestinal hyperacidity andulceration.

The compounds of this invention may be described by the general formulaI:

where:

Aralk is an arloweralkyl or substituted arloweralkyl R is a saturated orunsaturated acyclic member having from five to 12 carbon atoms, or asaturated or partially saturated carbocyclic member having from five to12 carbon atoms; and

X is a non-toxic inorganic or organic anion.

More specifically, the compounds of this invention may be described bystructural formula II:

where:

n is 1-2;

R is hydrogen, loweralkyl, loweralkenyl, cycloloweralkyl,cycloloweralkenyl, aryl (preferably phenyl, tolyl, xylyl, etc.) orarloweralkyl (preferably benzyl, etc.);

R R R R and R may be the same or different and are hydrogen, loweralkyl,halo, haloloweralkyl, nitro,

amino, monoand diloweralkylamino, acylamino, cyano, carbamyl, carboxy,carbloweralkoxy, loweralkoxy, haloloweralkoxy, hydroxy, acyl, haloacyl,acyloxy, phenoxy, halophenoxy, phenyl, halophenyl, thiocyanato,mercapto, loweralkylth io, loweralkylsulfinyl, loweralkylsulfonyl,haloloweralkylsulfonyl, sulfo, sulfonamido, sulfinamido,diloweralkylsulfonamido or halodiloweralkylsulfonamido;

R is a five to 12 carbon atom member which may be straight chained orbranched and is alkyl, alkenyl, cycloalkenyl, cycloalkyl,cycloalkylloweralkyl, spiroalkyl, bicyeloalkyl; and

X is a pharmaceutically acceptable nontoxic organic or inorganic anion(preferably chloride, bromide, iodide, sulfate, hy-

drogen sulfate, nitrate, phosphate, dihydrogenphosphate,monohydrogenphosphate, acetate, maleate, citrate, benzoate, lactate,benzenesulfonate, methanesulfonate, ethanesulfonate, etc.) The morepreferred compounds of this invention are also the more preferredcompounds which are useful in treating gastrointestinal disorders anddiseases and are described by the structural formula III:

it, in. m

where:

R,,, is hydrogen or loweralkyl; R R R R and R are hydrogen, halo, cyano,haloloweralkyl, nitro,

haloloweralkoxy, haloloweracyl, haloloweralkylsulfonyl orhalodiloweralkylsulfonamido; R is a five to 12 carbon atom member whichmay be straight chained or branched and is alkyl, alkenyl. cyc'loalkenylor cycloalkyl; and X" is chloride, bromide, iodide, nitrate, phosphateor sulfate. The most preferred compounds of this invention em- 6 bracethose compounds of structural formula III where:

R,, is hydrogen or methyl; R2, R3, R4, R5 and Re are hydrogen, fluoro,chloro, bromo, iodo, trifluoromethyl or nitro;

Ill

R is hexyl, heptyl, octyl. c-yclohexyl, cycloheptyl or In thedescriptive portions of this invention, the following definitions apply:The term lower alkyl" refers to a lower alkyl hydrocarbon groupcontaining from one to about eight carbon atoms which may be straightchained or branched.

The term lower alkenyl refers to a lower alkenyl hydrocarbon groupcontaining from one to about eight carbon atoms which may be straightchained or branched.

The acyl" radical may be any organic radical derived from an organicacid by the removal of its hydroxyl group, such as acetyl, propionyl,benzoyl, etc.

The lower alkoxy radical signifies an alkoxy group containing from oneto about eight carbon atoms which can be straight chained or branched.

The compounds of this invention can contain an asymetric carbon atomwhen n l and R is not H. For this reason, they may be obtained asracemic mixtures or as dextro and levorotatory isomers. These may beseparated by any of the various methods of resolution to obtain the d or1 compound. It is understood that these optical isomers are embracedwithin the scope of this invention.

Representative compounds of this invention which are particularly usefulare as follows:

trioctylbenzyl phosphonium chloride trioctyl(o-chlorobenzyl)phosphoniumchloride trioctyl(m-chlorobenzyl)phosphonium chloridetrioctyl(p-chlorobenzyl)phosphonium chloride Itrioctyl(p-trifluoromethylbenzyl)phosphonium chloride trioctyl(p-trifluoromethoxybenzyl)phosphonium chloridetriocty](p-dimethylsulfamylbenzyl)phosphonium chloridetrioctyl(2,3-dichlorobenzyl)phosphonium chloridetrioctyl(2,S-dichlorobenzyl)phosphonium chloridetrioctyl(3,4-dichlorobenzyl)phosphonium chloridetrioctyl(3,5-dichlorobenzyl)phosphonium chloridetrioctyl(2,3,4-dichlorobenzyl)phosphonium chloridetrioctyl(2,3,5-dichlorobenzy])phosphonium ridetrioctyl(2,3,6-dichlorobenzyl)phosphonium ridetrioctyl(2,4,5-dichlorobenzyl)phosphonium chloridetrioctyl(3,4,5-dichlorobenzyl)phosphonium ridetrioctyl(2,6-dichlorophenethyl)phosphonium chloridetrioctyl(2,6-dibromobenzyl)phosphonium bromidetrioctyl(2,4,6-trichlorobenzyl)phosphonium chloridetrioctyl(2,4,64ribromobenzyl)phosphonium bromidetrioctyl(2,6-dichlorobenzyl)phosphonium chloridetrioctyl(2,4-dichlorobenzyl)phosphonium chloride trioctyl(2,4-dibromobenzyl)phosphonium bromidetrioctyl(2,6-dichloro-a-methylbenzyl)phosphonium chloride trioctyl( 3,5-ditrifluoromethylbenzyl)phosphonium chloride trioctyl( 3.4,5-trimethoxybenzyl )phosphonium chloride trioctyl(2,4,6-trimethoxybenzyl )phosphonium chloride chlochlochlo- Itrioctyl(2,6-dibromo-4-fluorobenzyl)phosphonium bromide trioctyl(2,6-dichloro-4-thiocyanato be nzyl )phosphonium chloride trioctyl(2,6-dichloro-4-fluorobenzyl )phosphonium chloride trioctyl( 2,6-dibromo-4-iodobenzyl )phosphonium iodide trioctyl(2,6-dichloro-4-nitrobenzyl )phosphonium chloridetrioctyl(2,4-dichloro-fi-nitrobenzyl)phosphonium chloridetrioctyl(2,6-dibromo-4-nitrobenzyl)phosphonium bromide trioctyl(2,6-dichloro-4-cyanobenzyl )phosphonium chloride trioctyl(2,6,4-trichloro-4-dibenzyl )phosphonium chloride trioctyl( 2,6-dichloro-4-phenoxybenzyl )phosphonium chloride trioctyl( 2 ,6 ,4-trichloro-4-phenoxybenzyl )phosphonium chloridetrioctyl(2,6-dibromo-4-(4'-chlorophenoxy)benzyl)phosphonium bromidetrioctyl( 2,6-dibromo-4-p henoxy benzyl )phosphonium bromidetrioctyl(2,6-dibromo-4-chloro-4-dibenzyl)phosphonium bromidetriheptyl(2,-dichlorobenzyl)phosphonium chloridetriheptyl(2,6-dibromobenzyl)phosphonium brotrinonyl( 2,6-dichlorobenzyl)phosphonium chloride trinonyl(2,6-dibromobenzyl)phosphonium bromidetrihexyl( 2,fi-dichlorobenzyl)phosphonium chloride tricyclohexyl(2,6-dichlorobenzyl )phosphonium chloride tricycloheptyl(2,6-dichlorobenzyl )phosphonium chloride tricyclooctyl( 2,o-dichlorobenzyl )phosphonium chloridetrihexyl(2,4,6-trichlorobenzyl)phosphonium chloridetridecyl(2,6-dichlorobenzyl)phosphonium chloridetriundecyl(2,6-dichlorobenzl)phosphonium chloridetridodecyl(2,6-dichlorobenzyl)phosphonium chloridetrioctyl(2,6-dichlorobenzyl)phosphonium bromidetrioctyl(2,6-dichlorobenzyl)phosphonium iodidetrioctyl(2,6-dichlorobenzyl)phosphonium sulfatetrioctyl(2,6-dichlorobenzyl)phosphonium nitratetrioctyl(2,6-dichlorobenzyl)phosphonium phosphatetrioctyl(2,6-dichlorobenzyl)phosphonium acetatetrioctyl(2,6-dichlorobenzyl)phosphonium benzoate The compounds of thisinvention may be prepared by the following general procedures.

Condensation of a trisubstituted phosphine and an aralkylhalide resultsin the corresponding aralkyl trisubstituted phosphonium halide.

The following reaction equation illustrates this synthesis:

| R" R Ra Ra l R: R2

If. /R

| u n R R5 Re where n, R, R a ,R2, R R R and R are as described aboveand X is halogen.

The reaction is preferably carried out on the aralkyl bromide orchloride using a solvent and with increased temperatures.

The reaction is preferably carried out in an inert atmosphere preferablynitrogen or carbon dioxide. The solvent should be one that is misciblewith the reactants and is convenient to use the reactant halide inexcess as the solvent or alternatively a high boiling polar medium suchas phenoLacetonitrile, dimethylformamide, dimethylsulfoxide,methylethylketone, isopropanol, 2- nitropropane, etc. The reactiontemperature may vary from room temperature with readily reactivereactants to about 250C, although it is preferable to run the reactionat temperatures from about 50C to l50C. The isolation of the desiredphosphonium halide can be carried out by distilling off the solvent invacuo and precipitating the phosphonium halide by the addition of ahydrocarbon liquid such as n-pentane, n-hexane, cyclohexane, etc. Otheranions can be produced by exchange of the halide with alkali or alkalineearth salts containing the appropriate anion.

The starting materials employed in these foregoing methods are eitherknown compounds or they may be prepared by the following reactionsequences.

The benzyl and phenethyl halide starting materials can be convenientlyprepared by the following reactrons:

are as described it; 1;: Ha It:

Diazotization of an aromatic amine in the conventional manner followedby a Sandmeyer (a) type displacement produces the nitrile, which is thenhydrolyzed (b) to the carboxylic acid. Rosenmund reduction (0) of thecarboxylic acid results in the aldehyde which in turn is interacted withthe desired Grignard reagent and oxidized (d) to obtain the a-ketone.This may then either be reduced catalytically (e) to the a-substitutedbenzyl alcohol or a second Grignard reaction (f) may be carried out toobtain the a,a-disubstituted benzyl alcohol. Lithium aluminum hydridereduction of the benzoic acid (g) results in the benzyl alcohol.

The phenethylhalide starting materials may be prepared in an analogousmanner starting with the substituted a-phenylalkanoic acid.

Lithium aluminumhydride reduction (v) of the proper phenylacetic acidresults in the corresponding phenylethanol. This alcohol may also beprepared by catalytically reducing (w) the desired phenylacetaldehyde. AGrignard reaction (x) on the latter compound results in thea-substituted ketone which may then either be reduced catalytically (y)to the a-substituted phenethanol or a second Grignard reaction (2) maybe carried out to obtain the a,a-disubstituted phenethanol.

Appropriately desired end products having various R R R R and Rsubstituents can be prepared at various stages of the synthesis of thestarting materials by using suitable reactions in order to convert onegroup to another. Thus, for example, using conventional methods, ahalogen group can be treated under Rosenmund Von Brown conditions to thenitrile compound which in turn can be hydrolyzed to a carboxy. A nitrocan be reduced to an amino which can be alkylated to the dialkylaminosubstituent. A hydroxy compound can be prepared by demethylation of amethoxy substituent. A Sandmeyer type reaction can be carried out on anamino compound to introduce a chloro, bromo, xanthate, hydroxyl oralkoxyl group. The xanthate can then lead to the mercapto by hydrolysis,this turn can be alkylated to an alkylthio group which can be oxidizedto alkylsulfinyl and alkylsulfonyl groups. A thiocyanato group may bereduced to a mercapto. An iodo group may be removed by catalytichydrogenation.

Tertiary phosphines having the same groups may be prepared fromphosphorous halides with organometallic compounds by procedures known inthe art.

H-- ar For the preparation of tertiary phosphines with unlike groups,phospholhalo compounds may be reacted with an organometallic compound asabove. These may be obtained by alkali cleavage of phosphonium saltsaccording to conventional methods in the art. Thus, for example, withthe correct choice of starting materials tertiary phosphines with threeor, after quaternization, phosphonium salts with four different ligandscan be prepared.

We have found that the compounds of this invention have usefulanti-ulcerogenic properties. Further, they have an effective degree ofgastric anti-secretory activity, i.e., they reduce the volume and theacidity of the gastric fluid in humans and mammals. Still further,thesecompounds produce a considerable spasmolytic action on thegastrointestinal musculature, i.e., they reduce the peristaltic actionof the gastrointestinal musculature which is manifested by a delay ingastric emptying time.

Until now, the known anti-ulcerogenic compounds which showed gastricanti-secretory and gastrointestinal spasmolytic action have includedsuch agents as atropine, homatropine, propantheline, dicyclomine, etc.These compounds, however, cause accompanying undesirableanti-cholinergic properties such as mydriasis, xerostomia, cyclopegia,etc.

We have found that the phosphonium compounds of this invention areparticularly useful as anti-secretory, anti-spasmodic andanti-ulcerogenic agents because they are essentially devoid of theseunwanted effects.

In particular, the phosphonium compounds, as herein described, areuseful in the treatment of such gastrointestinal disorders and diseasesas duodenal ulcer and peptic ulcer.

For all these purposes, the phosphonium compounds of this invention canbe administered orally or parenterally, but they are preferablyadministered orally. Orally, they may be administered as tablets,aqueous or oily suspension, dispersible powders or granules, emulsions,hard or soft capsules, or syrups or elixirs. The term parenteral, asused herein, includes subcutaneous injection, intramuscular injection orinfusion techniques.

Compositions intended for oral use may be prepared according to anymethod known to the art for the manufacture of pharmaceuticalcompositions and such compositions may contain one or more agentsselected from the group consisting of sweetening agents, flavoringagents, coloring agents and preserving agents, in order to provide apharmaceutically elegant and palatable preparation.

Further, these compounds may be tableted or otherwise formulated so thatfor every 100 part by weight of the composition, there are presentbetween 5 and parts by weight of the active ingredient. The dosage unitform will generally contain between about 1 mg. and about 500 mg. of theactive ingredients of this invention. The preferred unit dose is betweenabout 10 mg. and mg.

The dosage regimen in carrying out the methods of this invention is thatwhich insures maximum therapeutic response until improvement is obtainedand thereafter the minimum effective level which gives relief. Thus, ingeneral, the dosages are those that are therapeutically effective in thetreatment of uicerogenic disease conditions or symptoms, such asduodenal and peptic ulcer. In general, the daily dose can be betweenabout 0.1 mg/kg and 50 mg/kg (preferably in the range of 1-25mg/kg/day). Bearing in mind, of course, that in selecting theappropriate dosage in any specific case, consideration must be given tothe patients weight, general health, age and other factors which mayinfluence response to the drug.

Various tests in animals have been carried out to show the ability ofthe compounds of this invention to exhibit reactions that can becorrelated with antiulcerogenic activity in humans. These tests involvesuch as the effect of the phosphonium compounds on gastric secretion,gastrointestinal spasm and their effect against ulcerogenic agents. Ithas been found that the compounds of this invention when tested in theabove variety of situations show a marked activity.

One such test is the gastric secretion test. This test is carried out asfollows. Shay rats are fasted for 4-8 hours, and water is given ad lib.The rats are selected at random and separated into groups of 10. Theanimals are treated intraduodenally (1.D.) with the test compound or thevehicle immediately subsequent to the ligation of the stomach at thepyloric sphincter. The animals are sacrificed with chloroform at 4 hourspostdrug administration, the stomach is removed and its contents areassayed for volume, pH and total acids.

A second gastric secretion test is carried out on dogs. This is outlinedin the Handbook of Physiology, Section 6: Alimentary Canal, Volume II:Secretion, American Physiology Society, Washington, D.C., 1967.

It has been found that the compounds of this invention when subjected tothe above gastric secretion tests display a marked ability to decreasegastric volume and gastric acidity. These tests are known to correlatewell with gastric activity in humans and is a standard test used todetermine anti-secretory properties.

To determine the anti-ulcer effectiveness, the follow ing test isemployed: Male Wistar rats 130150 grams) are fasted for 24 hours, thengiven reserpine at mg/kg i.p. Twenty-four hours later, the stomachs areremoved and examined for ulceration. Ulcers are graded on a 0-4 scaleand the number of ulcers is recorded. Pretreatment with the phosphoniumcompounds of this invention produces a decrease in ulcer grade and thenumber of ulcers compared to the control reserpinetreated rats.

Determination of anti-spasmodic properties can be carried out by theprocedure as outlined by D. A. Brodie and S. K. Kundrats in theirarticle entitled Effect of Drugs on Gastric Emptying in Rats, Fed. Proc.24:714 (1965).-

Mydriasis is detected by the procedure R. A. Turner, Screening Methodsin Pharmacology, Academic Press, New York, and London, pp. l745, 1965.Acute toxicity is calculated according to the standard Litchfield-Wilcoxon procedure.

In view of the results of these tests, the pharmacological data clearlyindicates that the phosphonium compounds of this invention can beconsidered to be effective anti-ulcerogenic, anti-secretory, andantispasmodic agents which are substantially free of anticholinergicside effects and having a low toxicity.

The following are detailed examples which show the preparation of thecompounds of this invention. They are to be construed as illustrationsof said compounds and not as limitations thereof.

Example 1 Tri-n-heptyl phosphine To a Grignard mixture ofn-heptylmagnesium chloride (0.43 mole) prepared from (10.9 g. ofmagnesium turnings and 57.5 g. of n-heptyl chloride) is added 132 g.(0.096 mole) of phosphorous trichloride in m1 of ether, in a nitrogenatmosphere, and 0C. The reaction mixture is allowed to warm to roomtemperature with stirring over 2 hours. This is then poured onto anice-cold saturated solution of ammonium chloride (250 ml) and themixture stirred for 1 hour. The aqueous layer is extracted with 200 mlof ether, dried over sodium sulfate, evaporated to dryness and distilledto give tri-n-heptyl phosphine (b.p. l44/0.l mm).

When n-heptyl chloride in the above reaction is substituted with thehalide of Table 1 below, then the corresponding product of Table [1below is prepared.

Table I n-pentyl chloride n-hexyl chloride n-octyl chloride n-nonylchloride n-decyl chloride n-undecyl chloride n-dodecyl chloride isoamylchloride Z-methyl-I-butenyl chloride cyclohex-2-enyl chloridecyclohex-3-enyl chloride cycloheptyl chloride cyclopentyl chloridecyclohexyl chloride cyclohexylmethyl chloride 3,5,5-trimethylheptylchloride 2-propylallyl chloridev 4-methyl-3-penten-1-y1 chlorideZ-methylheptyl chloride 3-methy1heptyl chloride Z-ethylhexyl chloride2,2,3,3-tetramethylbutyl chloride cyclooctyl chloride cyclooct-2-enylchloride bicyclo(3.2.1)oct-2-yl chloride iso-octenyl chloridespiro(3.4)oct-2-yl chloride Table I1 tri-n-pentyl phosphine tri-n-hexylphosphine tri-n-octyl phosphine tri-n-nonyl phosphine tri-n-decylphosphine tri-n-undecyl phosphine tri-n-dodecyl phosphine tri-isoamylphosphine tris-( 2-methyl- 1 -butenyl)phosphinetris-(cyclohex-2-enyl)phosphine tris-(cyclohex-3-enyl)phosphinetricycloheptyl phosphine tricyclopentyl phosphine tricyclohexylphosphine tricyclohexylmethyl phosphine tris-( 3 ,5 ,5 -trimethylheptyl)phosphine tris-( 2-propy1allyl )phosphinetris-(4-methyl-3-penten-1-yl)phosphine tris-(2-methylheptyl)phosphinetris-( 3 -methylheptyl )phosphine tris-( 2-ethylhexyl)phosphine tris-(2,2,3 ,3-tetramethylbutyl )phosphine tricyclooctyl phosphinetris-(cyclooct-2-enyl)phosphine tris-(bicyclo[ 3 .2. l]oct-2-yl)phosphine tri-(iso-octenyl)phosphine tri-(spiro[3.4]oct-2-y1)phosphine When phosphorous trichloride in the above exampleis replaced with dichloroheptylphosphine, dichlorocyclohexylphosphineand chlorodiheptylphosphine, then the starting materials prepared aredioctylheptylphosphine, dioctylcyclohexylphosphine anddiheptyloctylphosphine.

Example 2 Trioctyl(p-chlorobenzyl)phosphonium chloride To 25 g. (0.0675rnolehof tri-n-octyl phosphine dissolved in ISO-ml of acetonitrile in anitrogen atmosphere is added ll.9 g. (0.074 mole) of :,pdichlorotoluenedissolved in 50 m1 of acetonitrile. To the mixture is added 20 ml ofbenzene to cause solution. The mixture is then heated at refluxtemperature for 25 hours, cooled to room temperature and evaporated invacuo. The crude product is triturated with hexane, filtered, washed wthhexane, and dried to obtain trioctyl(p-chlorobenzyl) phosphoniumchloride (m.p.75.578C).

Example 3 Trioctyl(2,6-dichlorobenzyl)phosphonium chloride To 91 g.(0.245 mole) of tri-n-octyl phosphine in 500 ml of acetonitrile areadded 52.8 g. (0.27 mole) of 2,6- dichlorobenzyl chloride. The mixtureis then refluxed for l5 hours, concentrated in vacuo and the residueagitated with 3-200 ml of portions of hexane. The hexane is evaporatedto give trioctyl(2,6-dichlorobenzyl)phosphonium chloride (m.p.42"-44.5C).

When tri-n-octyl phosphine in the above example is substituted for thephosphines of Example 1, then the corresponding product below isprepared.

tri-n-pentyl(2,6-dichlorobenzyl)phosphonium chloridetri-n-hexyl(2,6-dichlorobenzyl)phosphonium chloridetri-n-heptyl(2,-dichlorobenzyl)phosphonium chloride tri-n-nonyl(2,6-dichlorobenzyl)phosphonium chloridetri-n-decyl(2,-dichlorobenzyl)phosphonium chloridetri-n-undecyl(2,6-dichlorobenzyl)phosphonium chloride tri-n-dodecyl(2,6-dichlorobenzyl )phosphonium chloride tri-isoamyl( 2,6-dichlorobenzyl)phosphonium chloride tris-(2-methyl-l-butenyl)(2,6-dichlorobenzyl)-phosphonium chloridetris-(cyclohex-2-enyl)(2,6-dichlorobenzyl)phosphonium chloridetris-(cyclohex-3-enyl)(2,6-dichlorobenzyl)phosphonium chloridetricycloheptyl(2,6-dichlorobenzyl)phosphonium chloridetricyclopentyK2,6-dichlorobenzyl)phosphonium chloridetricyclohexyl(2,6-dichlorobenzyl)phosphonium chloridetricyclohexylmethyl( 2 ,6-dichlorobenzyl )phosphonium chlorideHis-(3,5,S-trimethylhptylX2,6-dichlorobenzyl)- phosphonium chloridetris-(2-propylallyl 2,6-dich1orobenzyl)phosphonium chloride tris-(4-methyl-3-pentenl -yl)( 2,6-dichlorobenzyl)- phosphonium chloridetris-( 2- methylheptyl)(2,6-dichlorobenzy1)phosphonium chloride tris-(3-methylheptyl 2 ,-dichlorobenzyl )phosphonium chloride tris-(Z-ethylhexyl 2,6-dichlorobenzyl )phosphonium chloridetris-(2,2,3,3-tetramethylbutyl)(2,6-dichlorobenzyl )phosphonium chloridetricyclooctyl( 2,6-dichlorobenzyl )phosphonium chloridetris-(cyclooct-2-enyl)( 2,6-dichlorobenzyl )phosphonium chloridetris-(bicyclo[ 3.2.1 loct-2-yl)(2,6-dichlorobenzyl phosphonium chlorideI tri-(iso-octenyl)(2,6-dichlorobenzyl)phosphonium chloridetri-(spiro[3.4]oct-2-yl)(2,6-dichlorobenzyl)phosphonium chloridedioctylheptyl(2,6-dichlorobenzyl)phosphonium chloridediheptyloctyl(2,6-dichlorobenzyl)phosphonium chloridedioctylcycloheptyl(2,6-dichlorobenzyl)phosphonium chloride Example 4Trioctyl(2,6-dichlorobenzyl)phosphonium bromide 48 g. oftrioctyl(2,6-dichlorobenzyl)phosphonium chloride is added to 200 ml of asaturated aqueous sodium bromide solution. The mixture is then heated tothe solid is melted and the mixture is stirred for 5 min, cooled in anice-bath and the water decanted. Another 200 ml of saturated sodiumbromide solution is added and the procedure repeated. The ion exchangedphosphonium bromide is filtered, washed with 1 liter of water followedby 2-200 ml portions of hexane. The product is then heated twice with300 ml of distilled water until a melt, cooled and the water decanted,triturated with hexane, and dried to obtain trioctyl(2,6- dichlorobenzyl)phosphonium bromide (m.p.8 6-87.5C).

When the sodium bromide solution of the above example is replaced with asolution of an appropriate salt of Table 1 below, then the correspondingdesired phosphonium salt of Table ll below is obtained.

Table 1 sodium iodide sodium sulfate sodium nitrate sodium maleatesodium citrate sodium acetate potassium oxalate potassium bromide sodiumphosphate,

- l3 lithium bromide sodium benzoate sodium methanesulfonate Table IItrioctyl(2,6-dichlorobenzyl)phosphonium iodidetrioctyl(2,6-dichlorobenzyl)phosphonium sulfatetrioctyl(2,6-dichlorobenzyl)phosphonium nitratetrioctyl(2,6-dichlorobenzyl)phosphonium acetatetrioctyl(2,6-dichlorobenzyl)phosphonium oxalatetrioctyl(2,6-dichlorobenzyl)phosphonium bromidetrioctyl(2,6-dichlorbenzyl)phosphonium phosphatetrioctyl(2,6-dichlorobenzyl)phosphonium bromidetrioctyl(2,-dichlorobenzyl)phosphonium benzoatetrioctyl(2,6-dichlorobenzyl)phosphonium methanesulfonate ExampleTrioctyl(p-trifluoromethylbenzyl)phosphonium chloride To 14.8 g. (0.04mole) of tri-n-octyl phosphine suspended in 100 ml of acetonitrile isadded 9.7 g. (0.05 mole) of p-trifluoromethylbenzyl chloride in 75 ml ofacetonitrile. The reaction mixture is then heated at reflux for 24hours, cooled and evaporated to dryness in vacuo. The residue isdissolved in hexane:ether, treated with charcoal, filtered andconcentrated to dryness in vacuo to obtaintrioctyl(p-trifluoromethylbenzyl)phosphonium chloride.

When the starting materials of Table I below are used in place ofp-trifluoromethylbenzyl chloride in the above example, then thecorresponding product of Table [1 below is obtained.

Table I benzyl bromide benzyl chloride benzyl iodideP-trifluoromethoxybenzyl chloride p-trifluoroacetylbenzyl chlorideo-trifluoromethylbenzyl chloride p-trifluoromethylsulfonylbenzylchloride 3,5-dimethylbenzyl bromide o-chlorobenzyl chloridem-chlorobenzyl chloride p-chlorobenzyl chloridep-ditrifluoromethylsulfamylbeniyl chloride p-dimethylsulfamylbenzylchloride p-bromobenzyl bromide 2,6-dichloro-4-thiocyanatobenzyl chloride2,4-dichlorobenzyl chloride 2,3-dichlorobenzyl chloride3.4-dichlorobenzyl chloride 3,5-dichlorobenzyl chloride2,5-dichlorobenzyl chloride m-nitrobenzyl chloride p-nitrobenzylchloride p-dimethylaminobenzyl chloride o-methylbenzyl chloridem-methylbenzyl chloride p-methylbenzyl chloride p-cyanobenzyl chloridep-methoxybenzyl chloride p-hydroxybenzyl chloride p-carbethoxybenzylchloride o-methoxybenzyl chloride p-acetoxybenzyl chloridep-phenoxybenzyl chloride p-(4-chlorophenoxy)benzyl chloridep-methylthiobenzyl chloride p-dimethylsulfonamidobenzyl chloridea-cyclopropylmethylbenzyl chloride oz-ethylbenzyl chloride a-allylbenzylchloride benzhydryl chloride a-benzylphenethyl chloride2,6-dibromobenzyl bromide trifluoromethylbenzyl)phosphonium2,6-difluorobenzyl bromide 3,4,5-trimethoxybenzyl chloride2,4,6-trimethoxybenzyl chloride 3 ,5-dichlorobenzyl chloride2,4,6-trichlorobenzyl chloride 2,3,4-trichlorobenzyl chloride3,4,5-IliChl0I0benZyl cliloride 2,4,5-trichlorobenzyl chloride2,3,5-trichlorobenzyl chloride 2,3,6-trichlorobenzyl chloride2,4-dibromobenzyl bromide 2,4-difluorobenzyl bromide 2,4-dibromobenzylbromide 2-bromo-4-nitrobenzyl bromide 2,3,4-trimethylbenzyl chloride2,4,6-tribromobenzyl bromide 3,5-dibromobenzyl bromide3,5-difluorobenzyl bromide p-(4-chlorophenyl)benzyl chloride2,6-dichloro-4-trifluoromethylbenzyl chloride 2,5-dinitrobenzyl chloride2,6-dichloro-4-cyanobenzyl chloride 2,6-dichloro-4-thiocyanatobenzylchloride 2,6-dichloro-4-fluorobenzyl chloride p-acetamidobenzyl chloride2-methoxy-4-chlorobenzyl chloride 2,3,4,5,6-pentafluorobenzyl chloride2,3,5,6-tetrafluorobenzyl chloride p-phenylbenzyl chloride2,4-dichloro-6-thiocyanatobenzyl chloride 2,4-dichloro-6-nitrobenzylchloride 2-nitro-4-trifluoromethylbenzyl chloride2,6-dichloro-4-bromobenzyl bromide 3,S-ditrifluororhethylbenzyl chloride3,5-dichloro-4-methoxybenzyl chloride 2-chloro-4-trifluoromethylben zylchloride 2,6-dibromo 4-chlorobenzyl bromide 2-chloro-4-bromobenzylchloride 2,6-dibromo-4-nitrobenzyl bromide 2,6-dichloro-4-nitrobenzylchloride 2,6-dibromo-4-iodobenzyl iodide2,6-dibromo-4-trifluoromethylbenzyl bromide p-chloro-a-methylphenethylchloride afi-di-methylphenethyl chloride B-phenylphenethyl chloride2,6,4-trichloro-4-dibenzyl chloride 2,6-dichloro-4-phenoxybenzylchloride 5 2,6,4"-trichloro-4-phenoxybenzyl chloride2,6-dibromo-4-(4-chlorphenoxy)benzyl bromide 2,6-dibromo-4-phenoxybenzylbromide 2,6-dibromo-40-chloro-4-dibenzyl bromide Table II trioctylbenzylpho sphonium bromide trioctylbenzyl phosphonium chloride trioctylbenzylphosphonium iodide trioctyl(p-trifluoromethoxybenzy] )phosphonium l5chloride trioctyl(p-trifluoroacetylbenzyl)phosphonium chloridetrioctyl(o-trifluoromethylbenzyl)phosphonium chloride 0trioctyl(p-trifluoromethylsulfonylbenzyl)phosphonium chloridetrioctyl(p-dimenty(sulfamylbenzyl)phosphonium chloride Itrioctyl(3,5-dimethylbenzyl)phosphonium bromidetrioctyl(o-chlorobenzyl)phosphonium chloridetrioctyl(m-chlorobenzyl)phosphonium chloridetrioctyl(p-chlor'obenzyl)phosphonium chloridetrioctyl(p-di-trifluoromethylsulfamylbenzyl)phosphonium chloridetrioctyl(p-bromobenzyl)phosphonium bromidetrioctyl(2,6-dichloro-4-thiocyanatobenzyl)phosphonium chloridetrioctyl(2,4-dichlorobenzyl)phosphohium chloridetrioctyl(2,3-dichlorobenzyl)phosphonium chloridetrioctyl(3,4-dichlorobenzyl)phosphonium chloridetrioctyl(3,S-dichlorobenzyl)phosphonium chloridetrioctyl(2,5-dichlorobenzyl)phosphonium chloridetrioctyl(m-nitrobenzyl)phosphonium chloridetrioctyl(p-nitrobenzyl)phosphonium chloridetrioctyl(p-dimethylaminobenzyl)phosphonium chloridetrioctyl(o-methylbenzyl)phosphonium chloridetrioctyl(m-methylbenzyl)phosphonium chloridetrioctyl(p-methylbenzyl)phosphonium chloridetrioctyl(p-cyanobenzyl)phosphonium chloridetrioctyl(p-methoxybenzyl)phosphonium chloride trioctyl(p-hydroxybenzyl)phosphonium chloridetrioctyl(p-carbethoxybenzyl)phosphonium chloridetrioctyl(o-methoxybenzyl)phosphonium chloridetrioctyl(p-acetoxybenzyl)phosphonium chloridetrioctyl(p-phenoxybenzyl)phosphonium chloridetrioctyl[p-(4-chlorophenoxy)benzyl1phosphonium chloridetrioctyl(p-methylthiobenzyl)phosphonium chloridetrioctyl(p-dimethylsulfonamidobenzyl)phosphonium chloride 7trioctyl(a-cyclopropylmethylbenzyl)phosphonium chloride Itrioctyl(a-ethylbenzyl)phosphonium chloridetrioctyl(a-allylbenzyl)phosphonium chloridetrioctyl(benzhydryl)phosphonium chloride 65 trioctyl( a-benzylphenethyl)phosphonium chloride trioctyl(2,6-dibromobenzyl)phosphonium bromidetrioctyl(2,-difluorobenzyl)phosphonium bromide LII trioctyl(2,4-dibromobenzyl )phosphonium bromide trioctyl( 3,4,5-trimethoxybenzyl)phosphonium chloride trioctyl( 2,4,6-trimethoxybenzyl )phosphonium chloride trioctyl( 3,S-dichlorobenzyl)phosphonium chloridetrioctyl(2,4,6-trichlorobenzyl)phosphonium chloride trioctyl( 2 ,3,4-trichlorobenzyl )phosphonium chloride trioctyl( 3 ,4,S-trichlorobenzyl )phosphonium chloride trioctyl( 2 ,4,5-trichlorobenzyl )phosphonium chloride trioctyl(2,3,5-trichlorobenzyl)phosphonium chloride trioctyl( 2,3,6-trichlorobenzyl)phosphonium chloride trioctyl( 2,4-dibromobenzyl)phosphonium bromide trioctyl(2,4-difluorobenzyl)phosphonium bromidetrioctyl( 2-bromo-4-nitrobenzyl )phosphonium bromide trioctyl( 2,3,4-trimethylbenzyl)phosphonium chloride trioctyl(2,4,6-tribromobenzy1)phosphonium bromide trioctyl( 3 ,5 -dibromobenzyl)phosphonium bromide trioctyl( 3 ,5 -difluorobenzyl )phosphonium bromidetrioctyl[p-(4-chlorophenyl)benzyl]phosphonium chloride trioctyl( 2,6-dichloro-4-trifluoromethylbenzyl phosphonium chloride trioctyl( 2,5-dinitrobenzyl)phosphonium chloride trioctyl( 2,6-dichloro-4-cyanobenzyl)phosphonium chloride trioctyl( 2,6-dichloro-4-thiocyanatobenzyl)phosphonium chloride trioctyl( 2 ,6-dichloro-4-fluorobenzyl)phosphonium chloride trioctyl( p-acetamidobenzyl )phosphonium chloridetrioctyl( 2-methoxy-4-chlorobenzyl )phosphonium chloride trioctyl( 2,3,4,5 ,6-pentafluorobenzyl )phosphonium chloride trioctyl( 2,3 ,5,6-tetrafluorobe nzyl)phosphonium chloride trioctyl( p-phenylbenzyl)phosphonium chloride trioctyl( 2 ,4-dichlor'o-6-thioeyanatobenzyl)phosphonium chloride trioctyl( 2,4 -dichloro-6-nitrobenzyl )phosphoniumchloride trioctyl( 2nitro-4-trifl uoromethylbenzyl )phosphonium chloride7 trioctyl( 2,6-dichloro-4-bromobenzyl )phosphonium bromide trioctyl( 3,5 -ditrifluoromethylbenzyl )phosphonium chloride 7 trioctyl( 3 ,5-dichloro-4-methoxybenzyl )phosphonium chloride trioctyl(2-chloro-4-trifluoromethylbenzyl )phosphonium chloride trioctyl(2,6-dibromo-4-chlorobenzyl )phosphonium bromide trioctyl(2-chloro-4-bromobenzyl )phosphonium chloride trioctyl( 2 ,6-riitrobenzyl)phosphonium 4nitrobenzyl )bromide 17trioctyl(2,6-dichloro-4-nitrobenzyl)phosphonium chloridetrioctyl(2,6-dibromo-4-iodobenzyl)phosphonium iodidetrioctyl(2,6-dibromo-4-trifluoromethylbenzyl)- phosphonium bromidetrioctyl(2,6-dibromo-4-fluorobenzyl)phosphonium bromidetrioctyl(2,6-dichloro-a-methylbenzyl)phosphonium chloridetrioctyl(2,6-dichloro-a,a-dimethylbenzyl)phosphonium chloridetrioctyl(2,6-dichloro-a-phenylbenzyl)phosphonium chloridetrioctyl(2,6-dichloro-a-cyclohexylbenzyl)phosphonium chloridetrioctyl(phenethyl)phosphonium chloridetrioctyl(p-chlorophenethyl)phosphonium chloridetrioctyl[a-(cyclohex-2-enyl)benzyl]phosphonium chloridetrioctyl(a-tolylbenzyl)phosphonium chloridetrioctyl(a-xylylbenzyl)phosphonium chloridetrioctyl(oz-benzylbenzyl)phosphonium chloridetrioctyl(2,6-dichlorophenethyl)phosphonium chloridetrioctyl(p-chloro-a-methylphenethyl)phosphonium chloridetrioctyl(a,B-di-methylphenethyl)phosphonium chloridetrioctyKB-phenylphenethyl)phosphonium chloridetrioctyl(2,6,4-trichloro-4-dibenzyl)phosphonium chloridetrioctyl(2,6-dichloro-4-phenoxybenzyl)phosphonium chloridetrioctyl(2,6,4'-trichloro-4-phenoxybenzyl)phosphonium chloridetrioctyl[2,6-dibromo-4-(4-chlorophenoxy)benzyl]- phosphonium bromidetrioctyl(2,6-dibromo-4-phenoxybenzyl)phosphonium bromidetrioctyl(2,6-dibromo-4-chloro-4-dibenzyl)phosphonium chloride Example 6When the procedures of Examples 1-5 are followed but the startingmaterials are selected from Table 1, Example 3 and Table I, Example 5,then the following representative compounds are prepared.

tri-n-heptyl(p-trifluoromethylbenzyl)phosphonium chloridetri-n-hexyl(2,4-dichlorobenzyl)phosphonium chloridetricyclohexyl(p-chlorobenzyl)phosphonium chloride 18 tri-n-heptyl( 2,4-dichlorobenzyl )phosphonium chloridetri-n-heptyK2,5-dichlorobenzyl)phosphonium chloride tri-n-heptyl( 3,4-dichlorobenzyl )phosphonium chloridetri-n-heptyl(2,3,4,5,6-pentafluorobenzyl)phosphonium chloridetricyclohexyl(p-nitrobenzyl)phosphonium chloridetris-(3,5,5-trimethylheptyl)benzyl phosphonium chloridetri-n-dodecylphenethyl phosphonium chloridetri-n-heptyl[p-(4-chlorophenyl)benzyl]phosphonium chloridetri-(iso-octenyl)(B-phenylphenethyl)phosphonium chloride tri-n-pentyl(2,3,5-trichlorobenzyl )phosphonium chloridetridodecyl(p-chlorobenzyl)phosphonium chloridetris-(2,2,3,3-tetramethylbutyl)benzyl phosphonium chloridetri-n-heptyl[p-(4-chlorophenoxy)benzyl]phosphonium chloridetri-n-heptyl(2,6-dibromobenzyl)phosphonium bromidetri-n-hexyl(2,6-dibromobenzyl)phosphonium bromide tris-( 2-m ethylheptyl2 ,6-dibromobenzyl )pho sphonium bromide tris-( 2-methylheptyl)(p-triflubromethylbenzyU- phosphonium chloridetris-(cyclooct-2-enyl)(p-trifluoromethylbenzyD- phosphonium chloridetri-isoamyl(p-trifluoromethylbenzyl)phosphonium chloridetris-(2-methyl-1-butenyl)(p-trifluoromethylbenzyl) phosphonium chloridetri-n-hexyl(p-trifluoromethylbenzyl)phosphonium chloridetris-(spiro[3.4]oct-2-yy)(p-trifluoromethylbenzyl')phosphonium chloridetri-n-heptyl(p-phenoxybenzyl)phosphonium chloridetri-n-undecyl(2,6-dibromobenzyl)phosphonium bromide tris-(bicyclo[3.2. l]oct-2-yl)(p-trifluoromethylbenzyl) phosphonium chloride tri-n-heptyl( 3,4,5-trimethoxybenzyl)phosphonium chloride tris-(2-propylallyl)(p-chlorobenzyl )phosphonium chloridetriheptyl(2,4,6-tribromobenzyl)phosphonium bromidetriheptyl(2,6-dibromo-4-trifluoromethylbenzyl)- phosphonium bromidetrihepyl(2,6-dibromo-4-nitrobenzyl)phosphonium bromidetrinonyl(2,6-dibromobenzyl)phosphonium midetrihexyl(2,4,6-trichlorobenzyl)phosphonium chloride tricyclohexyl(2,6-dibromobenzyl )phosphonium bromide bro-tricyclohexy(p-chlorobenzyl)phosphonium chloride We claim: 1. A compoundof the formula is hydrogen; and

R and R are chloro. 4. A compound according to claim 1 where:

R1! is hydrogen; and R and R are bromo and R, is hydrogen,

bromo, trifluoromethyl, nitro, or iodo'. 5. A compound according toclaim 2 where:

R and R: are chloro, thus forming trioctyl(2,3-

dichlorobenzyl)phosphonium chloride. 6. A compound according to claim 2where:

R and R, are chloro, thus forming trioctyl(2,4-

dichlorobenzyl)phosphonium chloride. 7. A compound according to claim 2where: I 1

R, and R are chloro, thus forming trioctyl(2,5-

dichlorobenzyl)phosphonium chloride. 8. A compound according. to claim 2where:

R, and R are chloro, thus forming trioctyl(2,6-

dichlorobenzyl)phosphonium chloride. 9. A compound according to claim 2I where:

R; and R, are 'chloro, thus forming trioctyl(3,4-

dichiorobenzyl)phosphonium chloride. 10. A compound according to claim2' where:

. R, and R. are chloro, thus forming trioctyl(3,5-

dichlorobenzyl)phosphonium chloride. 11. A compound according to claim 2where:

R,, R, and R, are chloro, thus forming trioctyl(2,3,4-

trichlorobenzyl)phosphonium chloride. 12. A compound according to claim2 where:

R R and R, are chloro, thus forming trioctyl(2,3,5-

trichlorobenzyl)phosphonium chloride. 13. A compound according to claim2 where:

R,, R and R are chloro, thus forming trioctyl(2,3,6-

trichlorobenzyl)phosphonium chloride. 14. A compound according to claim2 where:

R,, R, and R are chloro, thus forming trioctyl(2,4,5-

trichlorobenzyl)phosphonium chloride.

15. A compound according to claim 2 where:

R R, and R are chloro, thus forming trioctyl(2,4,6,-

trichlorobenzyl)phosphonium chloride.

16. A compound according to claim 2 where:

R R and R are chloro, thus forming trioctyl(3,4,5-

trichlorobenzyl)phosphonium chloride.

17. A compound according to claim 1 where:

R R R and R are fluoro, Ra is hydrogen, R is octyl and X is chloride,thus forming trioctyl( 2,3,- 5,o-tetrafluorobenzyl)phosphonium chloride.

18. A compound according to claim 1 where:

R R R R and R are fluoro, R is hydrogen, R

is octyl and X is chloride, thus forming trioctyl( 2,-3,4,5,-pentafluorobenzyl)phosphonium chloride.

19. A compound according to claim 1 where:

R and R are ChlOl'O,,Ra is methyl, R is octyl and X is chloride, thusforming trioctyl(2,6-dichloroa-methylbenzyl)phosphonium chloride.

20. A compound according to claim 3 where:

R is hexyl and X is chloride, thus forming trihexyl(2-,6-dichlorobenzyl)phosphonium chloride.

21. A compound according to claim 3 where: l

R is heptyl and X is chloride, thus forming triheptyl-(2,G-dichlorobenzyl)phosphonium chloride.

22. A compound according to claim 3 where:

R is cyclohexyl and X is chloride thus fomingtricyclohexyl(2,6-dichlorobenzyl)phosphonium chloride.

23. A compound according to claim 3 where:

R is cycloheptyl and X is chloride, thus formingtricycloheptyl(2,6-dichlorobenzyl phosphonium chloride.

24. A compound according to'claim 3 R is cyclooctyl and X is chloride,thus forming tricyclooc'ty1( 2,6-dichlorobenzyl )phosphonium chloride.

25. A compound according to claim 3 R is octyl and X is bromide, thusforming trioctyl(2,-

o-dichlorobenzyl)phosphonium bromide.

26. A compound according to claim 3 where:

R is octyl andX is iodide thus forming trioctyl(2,6-dichlorobeniyl)phosphonium iodide. 27. A compound according to claim 4where:

R is hydrogen, R is octyl and X is bromide, thus forming'trioctyl(2,-dibromobenzyl)phosphonium 21 22 29. A compound according toclaim 4 trioctyl(2,6-dibromo-4-nitrobenzyl) phosphonium where: 1bromide.

R4 is trifluoromethyl, R is octyl and X is bromide, 32 A compoundaccording to claim 4 thus forming trioctyl(2,6-dibromo-4- where;"iflummehylbenzyl Phsphnium bmmide- 5 R is iodo R is octyl and xisiodide, thus forming gg compound according to Glam 1trioctyl(2,6-dibromo-4-iodobenzyl) phosphonium R2 and R6 are chloro, Ris trifluoromethyl, R is hyd l l drogen, R is octyl and X" is chloride,thus forming compoun accor mg to c aimtrioctyl(2,6-dichloro-4-trifluoromethylbenzyl)- 10 phosphonium chloride.R is trifluoromethyl, Ra IS hydrogen, R is octyl and 31. A compoundaccording to claim 4 X Chlonde, thus fomlmg Q yKP- where:trifluoromethylbenzyl)phosphonium chloride.

R is nitro R is octyl and X is bromide, thus forming

2. A compound according To claim 1 where: p1 R is hydrogen; R2, R3, R4,R5 and R6 are hydrogen or chloro; R is octyl; and X is chloride.
 3. Acompound according to claim 1 where: R is hydrogen; and R2 and R6 arechloro.
 4. A compound according to claim 1 where: R is hydrogen; and R2and R6 are bromo and R4 is hydrogen, bromo, trifluoromethyl, nitro, oriodo.
 5. A compound according to claim 2 where: R2 and R3 are chloro,thus forming trioctyl(2,3-dichlorobenzyl)phosphonium chloride.
 6. Acompound according to claim 2 where: R2 and R4 are chloro, thus formingtrioctyl(2,4-dichlorobenzyl)phosphonium chloride.
 7. A compoundaccording to claim 2 where: R2 and R5 are chloro, thus formingtrioctyl(2,5-dichlorobenzyl)phosphonium chloride.
 8. A compoundaccording to claim 2 where: R2 and R6 are chloro, thus formingtrioctyl(2,6-dichlorobenzyl)phosphonium chloride.
 9. A compoundaccording to claim 2 where: R3 and R4 are chloro, thus formingtrioctyl(3,4-dichlorobenzyl)phosphonium chloride.
 10. A compoundaccording to claim 2 where: R3 and R5 are chloro, thus formingtrioctyl(3,5-dichlorobenzyl)phosphonium chloride.
 11. A compoundaccording to claim 2 where: R2, R3 and R4 are chloro, thus formingtrioctyl(2,3,4-trichlorobenzyl)phosphonium chloride.
 12. A compoundaccording to claim 2 where: R2, R3 and R5 are chloro, thus formingtrioctyl(2,3,5-trichlorobenzyl)phosphonium chloride.
 13. A compoundaccording to claim 2 where: R2, R3 and R6 are chloro, thus formingtrioctyl(2,3,6-trichlorobenzyl)phosphonium chloride.
 14. A compoundaccording to claim 2 where: R2, R4 and R5 are chloro, thus formingtrioctyl(2,4,5-trichlorobenzyl)phosphonium chloride.
 15. A compoundaccording to claim 2 where: R2, R4 and R6 are chloro, thus formingtrioctyl(2,4,6,-trichlorobenzyl)phosphonium chloride.
 16. A compoundaccording to claim 2 where: R3, R4 and R5 are chloro, thus formingtrioctyl(3,4,5-trichlorobenzyl)phosphonium chloride.
 17. A compoundaccording to claim 1 where: R2, R3, R5 and R6 are fluoro, R is hydrogen,R is octyl and X is chloride, thus formingtrioctyl(2,3,5,6-tetrafluorobenzyl)phosphonium chloride.
 18. A compoundaccording to claim 1 where: R2, R3, R4, R5 and R6 are fluoro, R ishydrogen, R is octyl and X is chloride, thus formingtrioctyl(2,3,4,5,6-pentafluorobenzyl)phosphonium chloride.
 19. Acompound according to claim 1 where: R2 and R6 are chloro, R is methyl,R is octyl and X is chloride, thus forming trioctyl(2,6-dichloro- Alpha-methylbenzyl)phosphonium chloride.
 20. A compound according to claim 3where: R is hexyl and X is chloride, thus fomringtrihexyl(2,6-dichlorobenzyl)phosphonium chloride.
 21. A compoundaccording to claim 3 where: R is heptyl and X is chloride, thus formingtriheptyl(2,6-dichlorobenzyl)phosphonium chloride.
 22. A compoundaccording to claim 3 where: R is cyclohexyl and X is chloride thusfoming tricyclohexyl(2, 6-dichlorobenzyl)phosphonium chloride.
 23. Acompound according to claim 3 where: R is cycloheptyl and X is chloride,thus forming tricycloheptyl(2,6-dichlorobenzyl phosphonium cHloride. 24.A compound according to claim 3 where: R is cyclooctyl and X ischloride, thus forming tricyclooctyl(2,6-dichlorobenzyl)phosphoniumchloride.
 25. A compound according to claim 3 where: R is octyl and X isbromide, thus forming trioctyl(2,6-dichlorobenzyl)phosphonium bromide.26. A compound according to claim 3 where: R is octyl and X is iodidethus forming trioctyl(2,6-dichlorobenzyl)phosphonium iodide.
 27. Acompound according to claim 4 where: R4 is hydrogen, R is octyl and X isbromide, thus forming trioctyl(2,6-dibromobenzyl)phosphonium bromide.28. A compound according to claim 4 where: R4 is bromo, R is octyl and Xis bromide thus forming trioctyl(2,4,6-tribromobenzyl) phosphoniumbromide.
 29. A compound according to claim 4 where: R4 istrifluoromethyl, R is octyl and X is bromide, thus formingtrioctyl(2,6-dibromo-4-trifluoromethylbenzyl)phosphonium bromide.
 30. Acompound according to claim 1 where: R2 and R6 are chloro, R4 istrifluoromethyl, R is hydrogen, R is octyl and X is chloride, thusforming trioctyl(2,6-dichloro-4-trifluoromethylbenzyl)phosphoniumchloride.
 31. A compound according to claim 4 where: R4 is nitro , R isoctyl and X is bromide, thus forming trioctyl(2,6-dibromo-4-nitrobenzyl)phosphonium bromide.
 32. A compound according to claim 4 where: R4 isiodo , R is octyl and X is iodide, thus formingtrioctyl(2,6-dibromo-4-iodobenzyl) phosphonium iodide.
 33. A compoundaccording to claim 1 where: R4 is trifluoromethyl, R is hydrogen, R isoctyl and X is chloride, thus formingtrioctyl(p-trifluoromethylbenzyl)phosphonium chloride.